Fluoroalkoxide derivatives of thallium(i)



US. Cl. 260-429 4 Claims ABSTRACT OF THE DISCLOSURE The invention is novel thallium (I) polyfluoroalkoxides and a method for their preparation by reacting thallium(I) hydroxide and thallium(I) oxide with a polyfluoroalcohol.

This application is a continuation-in-part of co-pending application Ser. No. 685,967 filed Nov. 27, 1967 and now abandoned.

The invention herein described was made in the course of or under a contract with the Department of the Air Force.

SUMMARY The present invention relates to fluorine containing metal alkoxides and more particularly is concerned with thallium(I) polyfluoroalkoxides and to a method of their preparation.

The novel compounds of the present invention correspond to the formula TlOR wherein R is a polyfiuorinated straight or branched chain aliphatic group having a total of from 2 to about 11 carbon atoms, or a straight or branched chain polyfluorinated etherated aliphatic group having a total of from 2 to about 15 carbon atoms and being further characterized by containing 1 to about 5 ether linkages.

The compounds are either solids or, in some cases, liquids having a relatively high density at room temperature.

These fluoroalkoxide derivatives are suitable for use as herbicides and pesticides. Additionally, they find use as intermediates in the synthesis of other compounds in which a chloride, bromide or iodide ion is to be replaced by a fiuoroalkoxy group. Further, the low melting compounds which are liquids at relatively low temperatures, because of their relatively high densities, can be used as flotation liquids, as for example in a gyroscope or accelerometer.

The present compounds in which the R, groups contain 1 or more ether linkages are preferred for use as flota- United States Patent ice tion liquids in accelerometers due to their relatively low viscosities and high densities. The compounds in which the R; group is unetherated are preferred for use as flotation liquids in gyroscopes due to their relatively high viscosities and high densities.

In general, the compounds are prepared by reacting thallium(l) hydroxide (TlOH) or thallium(l) oxide (T1 0) with a fluoroalcohol of formula HOR;, where Rf is the same as set forth hereinbefore, using the fluoroalcohol in excess of that required stoichiometrically for formation of the alkoxide. The excess fluoroalcohol serves as a carrier liquid during the reaction. The corresponding thallium(I) fiuoroalkoxide compound readily is separated and recovered from the reaction mass.

DESCRIPTION OF PREFERRED EMBODIMENTS Preferred embodiments of the unetherated Compounds of the present invention comprise thallium(I) polyfluoroalkoxides of formula TlOR where R is a highly fluorinated aliphatic radical containing from 2 to about 11 carbon atoms. The thallium polyfluoroalkoxides corresponding to the formula TlOCH (CF CF H where n is an integer ranging from about 5 to about 9 are particularly preferred since these are relatively dense liquids at or slightly above room temperature.

Preferred embodiments of the etherated compounds of the present invention comprise thallium(I)polyfluoroalkoxides of formula TlOR where R, is a highly fluorinated aliphatic radical containing 2 to about 15 carbon atoms and containing 1 to about 5 other linkages. The etherated thallium(I) polyfluoroalkoxides containing 5 to about 12 carbon atoms and 1 to about 2 ether linkages are particularly prefeired since they have relatively low viscosities and relatively low freezing points as well as relatively high densities at room temperature.

The compounds ordinarily are prepared by reacting with agitation a thallium source material, i.e. thallium(I) hydroxide or thallium(l) oxide, with a fluoroalcohol (HOR in an inert substantially anhydrous atmosphere. Usually, the fluoroalcohol is employed in excess of that required stoichiometrically for reacting with the thallium(I) source material and is an amount sufficient to maintain the reaction mixture fluid during the reaction period. Alternatively, an inert carrier or diluent such as liquid aliphatic or aromatic hydrocarbons or halogenated hydrocarbons, for example, benzene, hexane, carbon tetrachloride and the like can be used. If a diluent is employed, about stoichiometric quantities of the thallium(l) reactant and fluoroalcohol preferably are used although an excess of either of these reactants does not detrimentally affect the reaction.

The quantities of excess fluoroalcohol or inert diluent to be used are not critical except that at a minimum the reaction mass must be sufiiciently fluid to be readily agitated. The maximum amount of carrier ordinarily is se- 3 lected so as to not require unduly large reactors and material handling equipment as well as to not provide an extremely dilute reaction mixture.

The reaction mixture is maintained at a temperature above the melting point of the fiuoroalcohol and below unreacted alcohol removed from the resulting filtrate 'by low pressure evaporation. The resulting thallium polyfluoroalkoxide product was further dried by pumping at a low absolute pressure (-0.l mm. Hg) at room temperature for 24 hours.

about a Period Of fffml about 1 to about 72 The product was recovered and its structure proved dy i the thalhum fluoroalkoxlfie Prod by elemental chemical analysis and infrared spectroscopy.

S i g i YC gf fli a l l'f i l if -h A number of the compounds identifymg charactenstrcs a on w1 ose uoroa co os w 1c are also were determined liquid at this temperature, using a reaction time of from about 4 to about 48 hours. (II) General preparation of etherated thallium (I) After the reaction period, diluent, if employed, or expolyfiuoroalkoxides cess fluoroalcohol is removed, as by low temperature evapm1l1l 1 e w1t 0 1 stirrer oration, and the thallium polyfiuoroalkoxide product dned g is s g zgg gf g 5 21? tchamum un u g g z zz g izz i gigggg g g g g g x g oxide and a stoichlometnc excess of an etherated fluoroa high purity. However, if desired the solid compounds alcohol i l g Stoppcred andhstlllljred at g temcan be further purified by recrystallization or other congerature t fee Unreacted t a X1 6 s n mov vent1onal purification techniques apparent to one skilled in ltered 0 under mtrpgen and a y W a Co 0 re the art by vacuum evaporation. The remaining product was ten The followin examples will serve to further illustrate transferred to a molecular and pulilfied bihdlsnnatlon at an absolute pressure of a out 0.00 mm. h 1 v ntlo 11n t 6 present n e H but are not Imam tol It It theleto In a slmilar manner, the reaction may be carried out using thallium I h droxide in place of thallium I oxide. EXAMPLES Y In both cases the product was recovered and its struc- (I) General preparation of unethemted thallium) ture proved by elemental chemical analys1s an d lnfrared l fl lk id spectroscopy. A number of the compounds identifylng characteristics also were determined.

A 100 milliliter round-bottom flask equipped with a Table I summarizes the reactants and their concentramagnetic stirrer was charged with a predetermined quantions to prepare a number of thallium polyfiuoroalkoxide TABLE I Thallium source Fluoroalcohol material reactant Grams Mole Type Grams Moles Product 10 0. 045 gctafiuoropcntalnoLnfl I179 gctgtluorotpentgxide.

10 0.045 rilluoroethano a ium ri uoroe 10Xl e.

10 0.045 PentatluoropropanoL... 30 0.200 Thallium pentafiuoropropoxide.

10 0.045 Hexafiu0r0is0propa1nol 26 0.214 ggalllium lliexafiftiloroistopropplxide.

10 0.045 Heptafluorobutano 1 0.205 a ium epta uoro utoxi e.

10 0 045 DodetgafiuproQ-methyl- 33 0.092 Thalliumdodeeafluor0-2-metl1y1-2-oetoxide.

2oe ano 0.225 Dodeeafluor0heptanol 265 0.800 Thallium dodeeafluoroheptoxide.

50 0.225 Hexadcealiuorononanal. 250 0.580 Thallium hexadeeafiuoronouoxide.

50 0.225 Pentadeeafluorooetanol. 190 0.475 Thallium pentadecafluorooetoxide.

10 0.045 Hexafl11oro-1,5-pen- 20 0.094 Thalliumhexafluoro-1,5-pentanedioxide.

tanecliol 11 0.05 PGI'IIIOIO-LIl-CPhYdTO- 16 0.031 Thallium perfluoro-l,l-dihydro-ZA-dimetl1yl-3oxapentoxide.

2,4 inlet 1y -3-oxapentanol.

12 T120 3.8 0.017 Perll'lolodtfl-dlizliuglfil0 9 0.015 Thallium perfiuoro-l,1-dihydr0-2,5-di1ncthyl-Bfidioxadecoxide.

2,5 hue y ioxadecanol. l3 T1011 6 0.027 Tr(iehfl1orometh31 ]lb1i)s 12 0.042 Thallium triehloromethylbls(trifluorometl1yl))methoxide.

tri uoromet y carbinol.

1 Preparation carried out at 75 C. in order to liquefy fiuoroalcohol reactant which melts at C. 2 Preparation carried out at 80 C. in order to liqueiy fluoroalcohol reactant which melts at 78 C.

tity of thallium hydroxide or thallium oxide and a stoichiometric excess of a fluoroalcohol. The flask was sealed and the contents stirred at room temperature for two days. After this period the reaction mixture was filtered compounds following the procedures set forth directly hereinbefore.

Table II presents analytical data and property characteristics for these compounds.

In the two tables, corresponding example numbers reunder a substantially anhydrous nitrogen atmosphere and fer to the same Compound preparation.

The compounds, except thallium heXafiuoro-1,5-pen tanedioxide, were soluble in benzene, acetone, diethyl ether and the fluoroalcohol reactant used in their preparation. Thallium hexafluoro-l,5-pentanedioxide is virtually insoluble in the above solvents. They are sensitive to mois- Infrared analysis of the novel compounds gave spectra which were consistent with the assigned structure.

These compounds are eflective herbicides for a number of weeds and the like vegetation. Additionally, these compounds have insecticidal and parasiticidal activity.

thallium dodecafluoroheptoxide, thallium hexadecafiuorononoxide and thallium pentadecafiuorooctoxide because of their low melting points and high densities have been shown to be suitable for use as stabilizing fluids for use in gyroscopes, for example. Thallium perfiuoro-l,1-dihydro-2,4-dimethyl-3-oxapentoxide and thallium perfluoro-l,1-dihydro-2,5-dimethyl-3, 6-dioxadecoxide are especially useful for use as flotation 20 fluids in accelerometers due to their high densities and In a manner similar to that described in preceding general Example I, other unetherated thallium fluoroalkoxides can be prepared by reacting thallium(I) hydroxide 5 or thal1ium(I) oxide with fluoroalcohols such as, for ex- HOC(CF C(CF OH HOCH (CF CF where x is an integer from 1 up to 6. In a manner similiar to that described in preceding general Example II, other etherated thallium fluoroalkoxides can be prepared by reacting thallium(I) hydroxide or thalliumfl) oxide with etherated fluoroalcohols such as, for example, HO(CH OCF (CF HOCH CF (CF O [CF CF CFg O C 1 where x is an integer from 1 to 3. The reaction of thallium(I) hydroxide or thallium(I) oxide with these fluoroalcohols will result in the formation of thallium(1) alkoxide corresponding to the formula TlOR wherein R; is 1,1-dihydro-3-trifiuorornethyl-2-oxabutyl, 1,1,2,2-tetrahydro 4 trifluoromethyl-3-oxapentyl, 1,1,2,2,3,3-hexahydro-5-trifluoromethyl-4-oxahexyl, perfiuoro 1,1 dihydro-2,5,8-trimethy1-3,6,9-trioxadodecyl, perfluoro 1,1- dihydro-2,S,8,1l-tetramethyl 3,6,9,12 tetraoxapentadecyl, perfluoro-l,1-dihydro-3,5,7-trimethyl 3,6 dioxanonyl, perfluoro-1,1-dihydro-2,5,8,IO-tetramethyl 3,6,9- trioxadodecyl or perfiuoro-Ll-dihydro 2,5,8,11 tetrarnethyl-3 ,6,9,12-tetraoxapentadecyl.

Various modifications can be made in the present invention wtihout departing from the spirit or scope thereof for it is understood that We limit ourselves only as de- 1. Thallium(I) polyfluoroalkoxides corresponding to (a) a polyfluorinated straight or branched chain aliphatic group having a total of from 2 to about 11 car- (b) a straight or branched chain polyfiuorinated etherated aliphatic group having a total of from 2 to about carbon atoms and being further characterized by containing 1 to about 5 ether linkages.

2. The thallium polyfluoroalkoxides as defined in claim 1 (a) wherein R is octafluoropentyl, trifiuoroethyl, pentafluoropropyl, hexafiuoroisopropyl, heptafluorobutyl, do-

decafiuoro 2 methyl-Z-octyl, dodecafluoroheptyl, hexadecafluorononyl, pentadecafiuorooctyl, 2,2,3,3,4,4-hexatrichloromethylbis(trifluoro- HH Hammad.

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